Dyestuff of the anthraquinone series



Patented Aug. 29,1933

DYESTUFF "oF THE ANTHRAQUINONE SERIES it a r Georg K ranzlein, Martin Corell, and Ernst Diefenbach,

Frankfort-on-the-cMain, Germany,

as'signors to General Aniline Works, Inc., New" York, N. Y., a corporationlof Delaware i No Drawing. Application October 30, 1931, Serial I No. 572,224, and in Germany Februaryfi, 1930 Thepresent invention relates to new dyestuffs of the anthraquinone series, more particularly it relates to new compounds of the following general formulaz A p I wherein R stands for hydrogen or'an alkyl radical, X means the sulfonic acid group and R1 means alkyl or an unsulfonated ar ylor' X stands for halogen and R1 for alkyl or a sulfonated or unsulfonated aryl, and the 000B group stands in one of the positions 5, 6, '7 and 8; Our new products are obtainable by condensing a 2;4-dihalogen-1aminoanthraquinohecarboxylic acid of the formula:

i lalogen wherein the COOH group stands'in one ofthe positions 5, 6, '1 and 8, or a salt thereof, with an aliphatic or aromatic amine. The condensation is preferably efifected by heating the alkali metal salts of the carboxylic acid together with the amine in the, presence of watenan. acid binding agent, such as sodium carbonate, and a small" .quantity of a catalytically acting substance, such as cuprous chloride, copper sulfate-and. the like. 1

The compounds, thus formed, are generally blue products. The compounds obtained from acid and an aromaticamine-with a sulfonating agenflyaluable water-solubleacid dyestuffs "of the followinggeneral f orm ula are produced 1; O A A. V A

. a S0511" Another way of preparing theseacid dyestuffs is by condensing a 2.4-dihalogen-l-aminoanthra- ;quinone-carboxy1ic acid with an aromatic amine which contains already asulf onic acid group; HIhe-compounds obtainable by condens'ing a acid with an ali ph' atic ,amine or, a sulfonated or: unsulionated aromatic amine'and represented'by. the general formula;

wherein Y represents the radical of an aliphatic amine or a sulfonated or unsulfonated radical of ,anaromatic amine, maybe transformed into comounds in which the''2-position"is occupied rbya sulfo'nic acid group byexchanging' the halogen atomv in the 2-position for a sulfonic acid group according 'to knownr'nethods, for instancafby 1 treatment with an alkali metal sulfite.

The above described newcompounds contain jing the free carboxylic acid group in one of the ,positions'fi, 6, Hand 8, a halogenat'om or the "smunsulfonated a ines are suitable'compounds for lfomc and group mthe lon, d a radical the production of lakes, due to the presence of' the salt-forming carboxylic acid group. They may also be used as dyestuffs for cellulose acetate of an aliphatic amine or afsulfonated or'unsulester compounds by .treatingthe compounds with an esterifying agent according to known methods,

for instance, with; an alcohol in the presence, of

dry hydrogen halide. Thecarboxylic ester compounds are valuable dyestuffs 0f goodfdyeing properties; 7 It is immaterial for, the productin of 2.4 dihalogen-1 aminoanthraquinone-carboxylic 2i p the new dyestufis whether the carboxylic acid group stands in 5-,'6-, 7- or 8-position of the anthraquinone nucleus.

As to the amines used for the preparation of our new compounds it is only essential that'a reactive hydrogen atom is present at the nitrogen atom.v Any primary or secondary amine of the 1 aliphatic or aromatic series is suitable for'the purpose of the present invention; 7 I

For the esterification of the carboxylic acid group any known method and esterifying agent 7 may be used.

thatdescribed in the preceding example by using The following examples serve to illustrate the invention,but'they are not-intendedto limit it being by weight, unless otherthereto, the parts wise stated: v

(1) 425 parts of 1-aminoanthraquinone2t4- dibromo-B-carboxylic acid are dissolved in 500 parts of "water and 12 parts of sodium carbonate. To this solution, there are added 2 parts of cuprous chloride and 10 partsof. aniline, whereupon I the whole is heated,. while stirring, at 90 C. to 100 C. until'the originally red colorof thereactionmixture has become blue. After cooling, the blue. compound thus formedis isolated by addition of an acid. The compound has .the'fo'llowing structural formula:

- O NH:

. sulfonating this 7 compound with fuming sulfuric acid of 10%strength at'60 C. to C.-, a dyestufi is obtained dyeing the animal fiber blue tints of good fastness properties. a The 'sulfonic acid has the following'probable'formula;

Compounds of similar properties are obtainable' by using in the above example, instead'of 1-aminoanthraquinonee2.4-dibromo-6-carboxylic acid, 1-aminoanthraquinone 2,4-dibromo '7-carboxylic acid. H

. The-reaction occurs in a manner analogous to other bases instead of' aniline. Thus; for instance, aliphatic amino-compounds maybe used,

such as methylamine, i ethylamine, 'propylamine 'or the like, furthermore aromatic, amino. compounds, for instance, those of the benzene'series, suchlas toluidines,cyclohexylamine or the like, bases of the naphthalene 'seriesysuchas naphthylamine, tetrahydro-naphthylamine or the like,

asl well 'as derivatives of theIbefore-mentioned V bases"? 7 Byusing instead of l-aminoanthraquinone- 2.4-dibromo-carboxylic acids the corresponding It has the following formula: I i

dichloro compounds, products are obtained which have a chlorine atom in the 2-position.

(2) 16 parts of 1-aminoanthraquinone-2- bromo-6-carboxylic-4-anilido sulfonic acid, obtainable according to Example 1, are suspended in 200 parts of absolute ethyl-alcohol. Dry

hydrogen chloride is introduced into thesuspension at boiling temperature. Hereby the compound gradually dissolves with formation of the carboxylic-acid-ethyl ester which-precipitates as the saturation with hydrogen chloride goes on. After some hours, the whole is allowed to cool, and the ester is filtered withsuction- In the dry state,;it is a blue powder, it dyes the animal fiber from an acid bath clear blue tints of good fastness to Washing and to fulling. The compound has the followingprobable formula;

v 'ozmo o o OaH. I I, i 7

By treating 1;aminoanthraquinone-2-bromo- '6-carboxy-4-anili'do-sulfonic acid with methylalcohol and hydrochloric acid, the corresponding 7 O NH; II I By treating this compound with fuming sulffuric acid of 20%. strength, thereis obtained a sulfonic acid-of the followingprobable formula:

. i 0 IITH V The dyestuff has properties similar to those of the sulfonic acid described in Example 1.

By treating the dyestuff in the manner described in Example 2 with ethylalcohol and hydrogen chloride, there is obtained the dyestuff 'of the following formula:

on: V a similar to those of the dyestufi obtainable according to Example 2.

(4) By treating l-amino-z bromo-fi-carboxy- 4-anilidoanthraquinone, obtainable according to Example 1, with neutral potassium sulfite in This dyestuif has properties phenol, the bromine atom in the 2-position is 'replaced by the sulfonic acid group and the 1- amino-6-carboxy- 4-anilidoanthraquinone- 2 -sul-- fonic acid is obtained. 16 parts of this sulfonic acid'are suspended" in 200 parts of absolute ethyl alcohol. While heating, dry hydrogenchloride is 1 introduced into this suspension. The ester, thus formed, precipitates, it is filtered with suction,

washed with alcohol and dried. It forms a blue powder, dyeing woolfroman acid bath fast blue tints of good fastnessproperties, especially of good fastness to washing and to fulling. The ester corresponds with the following formula:

CzEhOOC ll ONE strength and 2 parts of cuprous chloride. After cooling, the reaction mixture is acidified whereby the 1-amino-4-methylamino-6 -carboXylic acid of the formula 0 NE ll I .Iwherein means the sulfonic acid group and 135 radical of the benzene or naphthalene seriesfor i precipitates. It forms a blue compound, dyeing acetate-silk fastblue tints, I

Insteadof methylamine, other aliphatic amines may beused 1 1 (6) 37.5 parts of 1-amino-2--bromo-4-methyl+ aminoanthraquinone-6-carboxylic acid, obtainable according to "Example 5, aredissolved in 350 parts of concentrated sulfuric acid; to this solution, there are added drop by drop parts of absolute ethylalcohol, The formation of the ethyl ester is finished by heating the i solution at, v C. to C. Bycautiously pouring the solution on ice, the 'dye'stufl' is precipitated. ,It forms a violetish-blue powder which is no longer soluble insodium carbonate. Thedyestuif dyes acetate- 90 silk violetish-blue tints. It corresponds with the following formula: 5

' By treating this compound with potassium sulfite in phenol, the bromine atom in the 2-position is replaced by the sulfonica'cid group.

1. The compounds of the following general formula: i

nooo V r wherein R standsfor hydrogen or an alkyl radical, X means the sulfonic acid group and R1 an'alkyl radical or an unsulfonated radical of the benzene ornaphthalene series, or X stands for halogen and R1 .for an alkylradical or; a

sulfonated or unsulfonated radical. of the hen? zene or naphthalene series, said products-having generally a blue color. a

2. The acid dyestuffs of the general formula:.

R1 stands for an alkyl radical or an unsulfonated X stands for a halogen atom and R1 for asulfonated radical of the benzene or naphthalene series, andvwherein R represents an alkyl radical, saiddyestufl's dyeing the animal fiber blue tints.

3. The acid dyestuffs of the general formulap' Y wherein Xmeans the sulfonic acid group and R1 stands for an unsulfonated radical of the benzene series, or X stands for a bromine atom and: ,t

R1 for a sulfonated radical of the benzene series,

and R stands for methyl or ethyl, said dyestuffs dyeing the animal fiber bluetints. g V 4. The acid dyestufi of the. formula: V ;J l? ".NH2'

being in the dry state a blue powder, dyeingwool from an acid bath blue tints of good fastness, to 7 Washing and to fulling. s

5.7 The acid dyestufi of the formula:

NHg

being in the dry state a blue powder, dyeing wool from an acid bath clear blue tintsof good fastness to washing and to fulling.

6. 'Ihe acid dyestuif oi the formula v y being in the dry, state a blue powder, dyeing wool from an acid bath vblue tints of good fastness to Washing and to fulling.

7. The compounds of the following general fiormula: t

wherein R-sta'nds for hydrogen or an alkyl radical, X means the sulfonic' acid group and R1 means alkyl oran unsulfonated aryl, or 'X stands for halogen and Rl'fOI' alkyl or 'a sul:

fonatedor unsulfonated aryl, and the ---COOH group stands in one ofthe positions 5, 6, "7 and.8 1

said products havinggenerally a bluecolorfl j V r GEORG KRANZLEIN. I I v 'MARTIN CORELL.

ERNST DIEFENBACH. 

